Method of printing textiles using a printing paste containing beta-1,4 glucan

ABSTRACT

A PROCESS OF PRINTING WITH A COLORED PASTE COMPRISING FINELY-DIVIDED B-1,4 GLUCAN PARTICLES, A WATER-SOLUBLE BINDER AND A COLORING AGENT WHEREIN THE PASTE IS APPLIED TO A TEXTILE IN THE FORM OF A PATTERN AND THE TEXTILE IS SUBJECTED TO STEAM, WASHED AND DRIED.

United States Patent Office 3,679,352 Patented July 25, 1972 us. or. 8-62 6 Claims ABSTRACT OF THE DISCLOSURE A process of printing with a colored paste comprising finely-divided St-1,4 glucan particles, a water-soluble binder and a coloring agent wherein the paste is applied to a textile in the form of a pattern and the textile is subjected to steam, washed and dried.

At present, the textile industry employs roller printing methods and screen printing methods, but because of the trend toward diversification of colors and patterns, the emphasis has recently been placed on the screen printing methods. In the screen printing industry, there is a further trend of switching from manual printing to semiautomatic or fully-automatic printing with a view to increasing the printing speed, expecting at the same time to obtain by the wet-on-wet process a printing eflect equivalent to that obtained by the wet-on-dry process. Irrespective of whether a roller printing method or screen printing method is used, however, the textile printing industry is seeking to continue to improve the properties or quality of printing paste intended for higher printing efficiency and to respond to the change of the fabric materials to be printed. Since the fabric materials are getting more and more complicated and since blended yarns as well as blended fabrics are to be taken into consideration, the textile printing industry is required to use a very wide scope of sizing agents and printing pastes.

Under these circumstances, the printing paste has to play quite an important role in the printing of textile goods. In general, aqueous dye solutions are effective for the purpose of adhesion, but if it is intended to reproduce planned patterns exactly on the plane of textile fabrics, such dye solutions are not adquate because of their insufficient viscosity. The printing paste is used to overcome such difiiculty, namely to give suitable viscosity to the dye solution to increase the surface tension, thereby preventing the bleeding of color due to the capillary effect of the fibers and eifecting a partial dyeing limited to the design part. The printing effect depends largely on the fluidity of the printing paste, and the composition of such paste depends on the purpose of printing. But sharpness, permeative power, level printability, etc. are major factors to be considered in determining the composition of the printing paste.

Printing pastes used conventionally for textile printing include a large variety of thickening agents which are represented by various starches such as raw cake made of wheat gluten, starches of rice, corn and tapioca, etc., and polysaccharides or complex polysaccharides such as tragacanth, gum arabic, British gum, locust bean gum, crystal gum (karaya), sodium alginate and cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose and other water-soluble thickeners. Usually the colored paste used for textile printing is prepared by mixing dyes with one or a mixture of the thickening agents in water. In the case of printing fabrics made of natural or regenerated fibers by using such paste, the water given to the cloth at the time of applying the paste or subsequent steam-heating is absorbed by the cloth and the bleeding of dyes can be prevented fairly well because of the good hydroscopic property of the fiber itself. But in the case of printing hydrophobic fabrics like those made of synthetic fibers, excess water remains on the surface of the fabrics and dyes move into such excess water, causing bleeding of the dye. This results in unsatisfactory printing.

The bleeding of dyes may be prevented by the com bined effect of the pastes ability to prevent capillary phenomenon and the hygroscopic property of the cloth to be printed. it the cloth to be printed has low hygroscopic property, such cooperative effect is lost and the dye in the paste is caused to blur or run. Thus, in order to prevent such bleeding and to carry out trouble-free printing, it is desirable to substitute substances of high molecular weight for those having low molecular weight or to use a material which can give low viscosity with high concentration, thereby increasing the solid content of the colored paste. Actually, however, this procedure means using colored paste having a very high viscosity, .which is difiicult to prepare. Furthermore, since such paste is used in a large quantity, it is not easy to remove the paste by washing and the feed of fabric is impaired. Also the excessively high concentration of thickener reduces the permeation of colored paste into the cloth and reduces the evaporation speed of water, which makes it difiicult to employ the wet-on-wet method.

Accordingly, this invention concerns a process comprising printing a pattern on a textile fabric with a printing paste containing water-insoluble, finely-divided, organic particles at least 90% consisting of it-1,4 glucan, treating the textile fabric with steam, washing the textile to remove the paste and drying the textile.

This invention is an improvement over US. Pat. No.

' 3,259,537 to o. A. Battista.

The Water-insoluble, organic material is originally derived from cellulose-containing plant life, in most instances, wood, cotton, and bast or leaf fibers. In general, materials obtained from a halo-cellulose source are most useful, for example, ramie, flax, hemp, cotton, processed cellulose-containing material, for example, cotton linters, purified cotton, wood pulps such as bleached sulfite and sulfate pulps, regenerated forms of cellluose including rayon and cellophane, and the like. If the source material is too low in fi-1,4 glucan content, it is purified to remove nonessential or undesirable components such as pentosans, galactomannans, glucomannans, and the like, to provide a product containing at least and preferably at least 99% of 54,4 glucan.

The method of achieving finely-divided organic particles is not critical from the standpoint of this invention and will generally include, for example, mechanical disintegration, a combination of chemical degradation and mechanical attrition, chemical treatment only, precipitation from solution, and chemical regeneration. It is preferred on the basis of practical utility, that a combination of chemical degradation and mechanical attrition be used in forming the specified particle size of the water-insoluble ti-1,4 glucan-containing material.

Hereinafter, the term cellulose will be used to represent fi-1,4-glucan-containing materials for ease of explanation and illustration.

Chemical degradation of the cellulose material is brought about in a known manner to facilitate disintegration, for example, the material may be subjected to acid or alkali hydrolysis, or enzymatic treatment. One specific method of obtaining the desired result is reported in US. 2,978,446 issued Apr. 4, 1961, to O. A. Battista et al., wherein cellulose is subjected to a 2.5 normal aqueous solution of hydrochloric acid at boiling (about C.) for 15 minutes. This more drastic hydrolysis treatment provides a material which may be readily mechanically attrited in an aqueous medium with a nominal amount of energy. Similar treatments with mineral acids or alkali under more or less drastic conditions will produce attritable degraded cellulose using nominal or increased, energy for disintegration of the material to the proper particle The type of starting material prior to chemical degradation will also determine the amount or input energy for attrition of the cellulose to obtain the desired particle size.

For example, dilute hydrochloric acid hydrolysis of regenerated forms of cellulose will produce a material substantially all of which can be attrited to the desired particle size by merely dispersing the same with a conventional electrically driven kitchen beater in an aqueous medium for a few minutes. Other forms of cellulose, for example, wood pulp and cotton linters, after a similar hydrolysis treatment must be attrited with the same or more efiicient equipment for at least one half hour or more in an aqueous medium to provide a material at least a portion of which is within the desired particle size range. Mechanical attrition may be carried out by known techniques using for example, kitchen mixers, blenders, planetary mixers, ball mills, attrition mills, sonic mixers, high speed shearing devices and the like. In addition, the material may be forced through a multiplicity of fine'holes whereby it is subjected to a shearing action first by passage through said holes and thereafter by rubbing together of the various particles under the influence of applied force. The disintegration is preferably carried out in the presence of an aqueous medium to appreciably reduce the energy necessary to produce smaller particle sizes. The attrition should be extended to produce a mass wherein at least 30% and preferably over 80% of the particles measure no greater than about 0.4 micron.

As previously stated, regenerated forms of cellulose, for example, regenerated cellulose film, are easily brought to the prescribed particle sizeafter the controlled acid hydrolysis by merely dispersing the wet-cake material in water with a mixer. This will produce a stable dispersion wherein the dispersed particles are substantially all less than the prescribed 0.4 micron size. When wood pulp, cotton linters, and similar cellulose materials of greater molecular weight are hydrolyzed under controlled conditions and mechanically attrited in an aqueous medium, many large particles are present along with the desired small particles. When these cellulosic materials are dried after attrition they are ditficult to redisperse in water. It has been found that this type of material may be advantageously combined with a minor proportion of a specific barrier material to provide a readily redispersible mass.

Briefly, the barrier material is a specified sodium salt of carboxymethyl cellulose having a degree of substitution of from about 0.60 to about 0.90, and preferably having a viscosity in centipoises at 25 C. in a 2% aqueous solution of less than 18 up to about 800. The barrier may be combined with the finely-divided cellulose by drying a suspension of the cellulose particles in the presence of about 5 to of the barrier material. The combination 1 of barrier and cellulose particles is efiective for the purpose of this invention.

Particle sizes of the finely-divided cellulose of this invention when attrited and dispersed in an aqueous medium range up to about 1 1 microns or more but, when the finelydivided cellulose is dried, many of these smaller particles agglomerate to provide larger finely-divided cellulose particles ranging up to 100 microns or more. If the wet finelydivided cellulose from the aqueous dispersion is used herein to make printing paste, there will be no need to' separate larger particles and grind the paste for longer. periods to obtain a material which will not clog the printing screens. If, however, the dried cellulose or cellulose powder is employed to make paste, larger particles can be separated fromthe powder by sifting or the like and the paste must be ground for a longer length of time to break up the larger particle sizes. This will avoid clogging of the printing screens after repeated printing operations.

This invention proposes colored printing paste prepared by using the finely-divided cellulose as a substitute of a. portion of the water-soluble thickener in the paste or by adding it to a mixture of water-soluble thickener and dye solution. The amount of finely-divided cellulose which is incorporated in the printing paste ranges from about 1 to 30% based on the weight of the paste preferably from about 5 to 20%. In compounding the finely-divided cellulose it is not necessary, unlike water-soluble high polymer substances, to first prepare the master paste by using water. The finely-divided cellulose can be used in the form of a powder, which is added directly to the colored paste. This means that the mixing process requires no carrying of water and accordingly the paste absorbs water immediately and prevents the bleeding or running of color in the printing process.

The colored printing paste shows the following trend in its viscosity: In the case of using the finely-divided cellulose in place of a part of water-soluble thickener, the viscosity of the paste is definitely lower than that of a paste not containing it. In the case of adding the finelydivided cellulose to an aqueous mixture of water-soluble high polymer thickener and dye solution, the viscosity of the obtained colored paste increases somewhat according to the quantity of such addition, but the degree of such increase isfar smaller than in the case of incorporating additional Water-soluble thickener. Thus, the colored printing paste containing finely-divided cellulose has a characteristic that its viscosity behavior is not changed greatly by the quantity of said finely-divided cellulose employed. Table I shows the change in the viscosity of a colored paste in which the finely-divided cellulose was used in place of a portion of crystal gum and'Table II shows the change in viscosity of a colored paste when either the finely-divided cellulose was added or additional crystal gum was added to it.

If the colored printing paste prepared according to this invention is used, the depth of printed color on the product increases, and the prevention of blurring or running caused at the time of steam-heating, and the sharpness of color are improved. In steaming, the dye in the printing paste moves from the paste to the textile, along with water, to dye or print the textile. Furthermore, the colored printing paste of this invention reduces the strength of the film produced by the water-soluble high polymer substance thereby facilitating the permeation of water and making desizing easier. It is needless to say that the finely-divided cellulose used in this invention must have a size small enough to pass through the printing screen used during the printing operation.

The quantity of the finely divided cellulose to be added depends on the kind of paste material and of the cloth to be printed. It should be determined according to the purpose of printing. A standard type of printing screen mesh polyester fabric screen) was used for printing a fabric from which to judge the sharpness and bleeding of printing conducted by using the colored printing paste of this invention.

In the folowing examples, the sharpness of printing is represented by the height of a blank triangle reproduced by printing conducted using a standard printing screen, the original triangle pattern having dimensions of 0.3 cm. along the base and 10 cm. in height. A greater height of the reproduced triangle means better sharpness, the best sharpness being represented by a measurement of 95 mm. for the printed triangle.

The dye bleeding after printing and steaming is represented by the length of the base of the above-mentioned triangle. Accordingly, a greater length of the base indicates a greater bleeding. The optimum bleeding condition is represented by a measurement of 2.7 mm. for the printed triangle.

EXAMPLE I 500 g. of an oil-inwater type emulsion was prepared by using 73% kerosene in water. Also, 500 g. of a 30% crystal gum solution in water was prepared. 50 g. each of the emulsion and solution were mixed with each other and kneaded in a mortar to prepare a paste to be used as the master paste.

Separately, 20 g. of a dye (Foron Red S- FL, Color Index nameDisperse Red 72) and 20 g. of a dye solvent (Glysolve AOX, a thioethylene glycol) were weighed and put into 460 g. of hot water at 80 C. to dissolve the dye uniformly.

50 g. each of the master paste and the dye solution were transferred into a 100 ml. beaker. Several kinds of this mixture were prepared, one without addition of any finely-divided cellulose and others with the addition respectively of and g. of finely-divided cellulose.

The finely-divided cellulose was prepared by the acid hydrolysis and attrition of regenerated cellulose waste to obtain a product dispersed in an aqueous medium wherein 66% of the particles were under 0.2 micron and substantially all were under 1 micron. These particles were spray dried to obtain a powdery product having an average particle size range of from about 50-75 microns.

Each of these mixtures was stirred for three minutes in a homomixer to prepare colored printing paste for textile printing.

Printing tests were conducted with the above-mentioned two kinds of colored printing paste by using a standard printing screen on a woven polyester textile cloth. The printed cloth was air-dried, then steam-heated at 130 C. for 30 minutes by application of the steam in direct contact with the cloth, and then washed with water. The cloth was then scoured at 70 C. for 30 minutes with 2 g./l. of Scourol No. 400a high molecular weight polyethylene glycol with addition of caustic soda (0.5 .g./l.) and hydrosulfite (0.5 g./l.), washed with water and left to dry and then finished with ironing.

The sharpness, bleeding and depth of color were judged with unaided eye and also measured numerically.

The results of such observation and measurement are shown in Tables III and IV from which it can be seen that the printing with the colored printing paste containing the finely-divided cellulose gives far better results in every printing property.

TABLE III.RESULTS OF UNAIDED EYE OBSERVATION OF PRINT PATTERN TABLE IV.RESULTS 0F MEASUREMENT OF BLANK TRIANGLE PRINT ment it is clear that there is a big difference in the sharpness and bleeding properties between the printings conducted with printing paste with and without addition of the finely-divided cellulose.

EXAMPLE II A colored printing paste was prepared with the following composition:

Percent Dye (Sevron Brilliant Red B, Color Index Name Cationic Red 15) Dye Solvent (Glysolve AOX, a thioethylene glycol) 2 Acetic acid 1 Tartaric acid (50% solution) 2 Hot water 43 Master paste (rice paste used in traditional Japanese Yuzen silk-printing) 50 50 g. each of this colored printing paste was weighed separately into five mortars, to which finely-divided cellulose as described in Example I Was added in a ratio of 0, 5, 10, 15 and 20% respectively to the colored paste. After mixing and kneading these mixtures sufficiently with a pestle, printing was conducted with these colored printing pastes on woven acrylic textile cloth in the same manner as set forth in Example I. The printed cloth was air-dried and then steam-heated in an autoclave at C. for 30 minutes such that the steam was in direct contact with the cloth. After completing the steam-heating, the cloth was washed well with water, treated with 2 g./1. Marseilles soap solution at 60 C. for 20 minutes and washed again with water well. The cloth was then airdried and finished by ironing. Printing effect was compared by observation with unaided eye and by measurement. The results are given in Table V which indicate that sharpness and prevention of bleeding were both improved by the addition of the finely-divided cellulose.

In the same manner as shown in Example I, a 70% oil-in-water (O/W) kerosene emulsion and a 50% aqueous crystal gum solution were prepared separately, and the following master paste compositions were prepared with the addition of finely-divided cellluose as described in Example I in various ratios:

TABLE VI Finely- 50% divided 70% crystal cellulose kerosene gum added Sample No emulsion solution (percent) With these master pastes, the following composition of colored printing pastes were prepared:

Printing was conducted with these colored pastes on nylon cloth in the same manner as shown in Example I.

After air-drying, the printed cloth was steam-treated in an autoclave at 100 C. for 30 minutes, such that the steam was in direct contact with the cloth. The cloth was then washed well with water and treated with 2 g./l. Scourol No. 400, a high molecular weight polyethylene glycol at 70 C. for 20 minutes. Then it was washed with water, air-dried and finished by ironing.

The sharpness of printing, bleeding characteristics anddepth of printed color were measured. The results are given in Table VI which indicates that the printing effect was improved by the addition of the finely-divided cellulose.

TABLE VII Color Sample N o. Sha pness Bleeding depth (from Table VI) (mm.) (mm) percent Here the depth of color was determined by measuring the rate of light passage, by means of a photoelectric photometer, of the extracted solution that has been obtained by extraction with pyridine of a certain area of printed part of each sample. Accordingly, a larger value represents lower color depth.

EXAMPLE IV Two kinds of paste were prepared with the following (B): Above paste+10 parts of finely-divided cellulose as described in Example I.

Ten kinds of colored printing paste were prepared from the paste made above with addition of two parts each of 8 various cationic dyes, and 10-color wet-on-wet printings were conducted on acrylic cloth by the use of an autoscreen printing machine. After drying, the printed cloth was steam-heated at 105 C. for 40 minutes such that the steam was in direct contact therewith, and treated with 300 times as much water in a washing machine. After removing water, the cloth was treated with 2 g./l. Marseilles soap solution at C. for 20 minutes, further treated again with 300 times as much water for 10 minutes, dried and finished by ironing.

The feel of the two kinds of cloth printed with printing pastes was compared by the hand of ten inspectors. All of the inspectors recognized that the cloth printed with colored printing paste containing finely-divided cellulose had better feel in the printed part than that printed without it.

The cloth printed with paste containing finely-divided cellluose also showed less soil than the other.

The cloth printed with printing paste containing finelydivided cellulose showed no bleeding at the borders between diiferent colors, while the other showed bleeding.

Various changes and modifications may be made practicing this invention without departing from the spirit and scope thereof and therefore the invention is not to be limited except as defined in the appended claims.

We claim: A

1. A process comprising printing a pattern on a textile fabric with a printing paste containing water-insoluble finely-divided organic particles at least consisting of 184,4 glucan in an amount sufiicieut to improve the clarity and color depth of the resulting print, treating said textile fabric with steam, washing the textile to remove the paste and drying the textile.

2. The process of claim 1 wherein the amount of organic particles in the printing paste ranges from 5 to 20% based on the weight of the paste.

3. The process of claim 1 wherein the paste is dried on the textile fabric before the steam treatment.

4. The process of claim 1 wherein finely-divided organic particles are added to the printing paste in the dry state.

5. The process of claim 1 wherein the textile fabric comprises hydrophobic fibers.

6. The process of claim 1 wherein the textile fabric is dry when the printing paste is applied thereto.

References Cited UNITED STATES PATENTS 3,485,572 12/1969 Taube 862 3,259,537 7/1966 Battista 161-146 DONALD LEVY, Primary Examiner US. Cl. X.R. 8-83 

